JPH02187417A - Packed spraying polyurea elastomer - Google Patents

Abstract

PURPOSE: To provide the subject elastomer which has a high curing speed and efficiently gives many kinds of moldings by spraying together a component containing an aromatic polyisocyanate and a component containing a specific polyol, and by dispensing filler material into a spray pattern.

CONSTITUTION: An objective elastomer is obtained by spraying and mixing together a reaction flow containing (A) an aromatic polyisocyanate [preferably methylene-bis(4-phenyl) isocyanate] and a reactive flow containing (B) an amine- terminated polyether which is produced by reductive amination of polyol and has a molecular weight of 1,500 or higher and in which 50% or more of active hydrogens have a shape of amine hydrogen and (C) a chain-extending agent (preferably 1-methyl-3,5-diethyl-2,4-diamino benzene or the like), and by dispensing filler material (preferably chopped glass) into a spray pattern of the obtained 2-component polyurea elastomer.

COPYRIGHT: (C)1990,JPO

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to the production of spray elastomers.

[Prior Art] In US-A-3,979,364, aminated polyethers are used as a component together with polyols to make elastomers, as used below. US
No. -A-3666788 describes the use of cyanoalkylated and aminated polyethers in spray systems. In column 1 of US-A-3,666,788 it is stated that aminated polyethers such as those used below cannot be used in spray coatings because they react very rapidly with incyanates. It is being

US-A-4396729, -4444910 and -4
433067 is a high molecular weight amine-terminated polyether;
Aromatic diamine chain extenders and aromatic polyisocyanates (these may simply be polyisocyanates,
or a quasi-prepolymer prepared from a polyol reacted with a polyisocyanate in which the incyanate groups remain unreacted). Various patents, such as US-A-4607090, describe the above-mentioned basic combination as well as mold release agents and other additives such as catalysts and fillers including glass fibers.

No. 4,585,850 discloses glass flakes pretreated with amino-terminated polyethers having more than 50% active hydrogen in the form of amine hydrogens and an average molecular weight of more than 1500, chain extenders, amino cyan coupling agents, The present invention also relates to a reaction injection molded elastomer made by reacting an aromatic polyisocyanate in a closed mold.

US-A-4585850 is, for example, US-A-44
Includes discussion of other patent applications and patents in this field, such as No. 74,900 and No. 4,507,090.

“Reinforced High Elasticity RI” by E. G. Schwartz et al.
Effect of silane and machining in M-urethane composites” [Journal of Elastomers & Plastics
ofElastomers and Plastics
), Volume 11, October 1979, describes the use of silanized crushed glass fibers in reinforced RIM composites.

Article by Ed Galli rRRIM Surface Modification for Urethane [Plastic Compounding (Plastic Compounding (Plastic Compounding)
plastics compounding) (19
[1982/1982] discloses reinforcement of RRIM urethane with silanized glass fibers.

Co-pending application cylinder 07 filed April 16, 1987
No. 1039.035 discloses a polyurea spray system for coating strands and/or wires.

SUMMARY OF THE INVENTION The present invention provides a method for making a sprayed polyurea elastomer in combination with a filler that includes the steps of simultaneously spraying two reactive streams to deliver the filler in a spray pattern. One of the two reactive streams contains an aromatic polyisocyanate, and the other reactive stream contains an aromatic polyisocyanate having a molecular weight of 1500 or more and in which 50% or more of its active hydrogens are in the form of amine hydrogens. a method characterized in that it comprises an amine-terminated polyether and a chain extender;
Regarding. The invention also relates to the resulting spray elastomer.

In the present invention, the average molecular weight is 1500 or more and the functionality is 2 to 2.
6 preferably 2 to 3, and the amine equivalent weight is 750 to
Amino-terminated polyethers are effective, including primary and secondary amine-terminated polyether polyols that are 4,000.

Mixtures of amine-terminated polyethers can also be used. The particular amine-terminated polyether chosen will depend on the desired physical properties of the elastomer. These materials can be made by various methods known in the art.

Examples of amino-terminated polyethers useful in the present invention are polyether resins prepared from a suitable initiator to which a lower alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, has been added; The resulting hydroxyl-terminated polyol is aminated. If more than one oxide is used, these can be present as blocks of one or the other polyether or as a random mixture. In the amination step, it is highly desirable that the terminal hydroxyl groups within the polyol be substantially all secondary hydroxyl groups to facilitate amination. Usually, aminated Danda does not completely replace all of the hydroxyl groups, but most of the hydroxyl groups are replaced by amine groups. Thus, the amine-terminated boether resins useful in this invention have more than 50 percent of their active hydrogens in the form of amine hydrogens. When ethylene oxide is used, it is desirable to cap the hydroxyl-terminated polyol with a small amount of higher alkylene oxide so that the terminal hydroxyl groups are essentially all secondary hydroxyl groups.

The polyol thus prepared can then be used, e.g.
Reductive amination is carried out by prior art techniques as outlined in S-A-3654370.

A single high molecular weight amino terminated polyether resin can be used in the practice of this invention.

Alternatively, mixtures of high molecular weight amino-terminated polyols may be used, such as mixtures of di- and trifunctional materials and/or mixtures of materials of different molecular weight or different chemical composition.

Examples of the chain extender used in the present invention include l-methyl-3,5-diethyl-2,4-diaminobenzene,
1-Methyl-3,5-diethyl-2,6-diaminobenzene (both of these materials are also called diethyltoluenediamine or DETA), 1.3.5-1-liethyl-2.6-diamitbenzene, and 3. .5.3', 5'
-tetraethyl-4,4'-diaminodiphenyl-methane. A particularly preferred aromatic diamine chain extender is 1-methyl-3,5-diethyl-2,4-diaminobenzene or a mixture of this compound and 1-methyl-3,5-diethyl-2,6-diaminobenzene. . US-A
It is within the scope of this invention to include some aliphatic chain extenders such as those noted in -4246363 and -4269945.

Other chain extenders that can be used in the process of the invention are low molecular weight polyoxyalkylene polyamines containing terminal amine groups having the following chemical formula: H3 "where x+y+z is about 5.3 .

The average amine hydrogen equivalent is approximately 67 and this product is JEFFA
Texaco Chem as MINE T-403
It is commercially available from ical Company. Another related polyoxypropylene polyamine has the formula: where X is about 2.6 or about 5.6.

A product where X is about 5.6 has an average amine hydrogen equivalent weight of about 100 and is designated as JEFFAMINE T-400
Exaco CI+emicaL Company.

The product having an average amine hydrogen equivalent weight of about 57.5 is commercially available as JIE "FAMINE T-230" from Texaco Chemical Company.

Other chain extenders will be apparent to those skilled in the art, and the above description is not meant to be limiting to the invention claimed herein.

A wide variety of aromatic polyisocyanates can be used. Typical aromatic polyisocyanates include p-phinyl diisocyanate, polymethylene polyphenylisocyanate, 2,6-toluene diisocyanate,
Dianisidine diisocyanate, bitriene diisocyanate, naphthalene-1,4-diisocyanate, bis(4-incyanatophenyl)methane, bis(3-methyl-3-incyanatophenyl)methane, bis(3-methyl-4-incyanato) phenyl)methane, and 4,4
'-diphenylpropane diisocyanate.

Other aromatic polyisocyanates that can be used in the practice of this invention are methylene crosslinked polyphenyl polyisocyanate mixtures having a functionality of 2 to 4. These latter incyanate compounds are
It is generally prepared by the phosgenation of the corresponding methylene-bridged polyphenylpolyamine, which is conventionally prepared by the reaction of a primary aromatic amine such as aniline with formaldehyde in the presence of hydrochloric acid and/or other acidic catalysts. Ru. Known processes for the production of polyamines and the corresponding methylene-bridged polyphenyl polyisocyanates therefrom are described in the academic literature as well as in US-A-26837.
No. 30, -2950263, -3012008, -
It is described in a number of patents, such as No. 3,344,162 and -3,362,979.

Typically, methylene crosslinked polyphenyl polyisocyanate mixtures contain from 20 to 100 weight percent of isomers of methylene diphenyl diisocyanate, the remainder of which is polymethylene polyphenyl diisocyanates with higher functionality and higher molecular weight. It is. Typical of these are methylene diphenyl diisocyanate isomers (20-95% by weight of 4
．． A mixture of polyphenyl polyisocyanates containing 1% by weight of 20 to 100 polymethylene polyphenyl 4'-isomers, the remainder having a high molecular weight and an average functionality (value) of 2.1 to 3.5. They are polyincyanates. These isocyanate mixtures are known commercially available substances and can be prepared by the method described in US-A-3,362,979.

By far the most preferred aromatic polyisocyanate is methylene bis(4-) enyl isocyanate, or MDI.

Pure MD1. Quasi-prepolymer of MDI, modified pure MD
I and the like are also useful. This type of material has a suitable RI
Since pure MDI, which can be used to produce M elastomers, is solid and therefore often inconvenient to use, MDI-based liquid products are often used, and these are the ones used in the present application. It is included within the term MDI or methylene bis(4-phenylisocyanate). US-A-3394164 discloses an example of a liquid MDI product. Furthermore, for boat fishing, pure MIO modified with uretonimine is also included. This product is made by heating pure distilled MDI in the presence of a catalyst. Liquid products include pure MDI and modified MDI.
is a mixture of DI; OCN@CH2@N=C=N CH20-NC0+CO
ir uretonimine Examples of commercially available substances of this type include D
ow's l5ONATE l25M (pure MDI)
and rsONATE 143 L (r liquid JMDI)
It should be understood that the term polyisocyanate includes the use of isocyanates in stoichiometric amounts, or alternatively in excess of stoichiometric amounts, based on all components in the formulation. Quasi(q) of polyisocyanates with active hydrogen-containing substances
Also included is a uasil prepolymer.

Although the reactants usually do not require a catalyst, the following catalysts can be used if necessary. Catalysts such as tertiary amines or organotin compounds or other polyurethane catalysts are used. The organotin compound is suitably a stannous or stannous compound, such as a stannous salt of a carboxylic acid, a trialkyltin oxide, a dialkyltin dihalide, a dialkyltin oxide. Here, the organic group of the organic part of the tin compound is a hydrocarbon group containing 1 to 8 carbon atoms, such as dibutyltin dilaurate,
Dibutyltin diacetate, diethyltin diacetate, dibutyltin diacetate, di-2-ethylhexyltin oxide, dioctyltin dioxide, stannous ofcunate,
Stannous oleate and the like or mixtures thereof can be used.

Examples of tertiary amine catalysts include trialkylamines (e.g., trimethylamine, triethylamine), N-alkylmorpholines (e.g., N-methylmorpholine, N-ethylmorpholine, dimethyldiaminodiethyl ether, etc.), 1,4-dimethylpiperazine, triethylenediamine. Heterocyclic amines such as: and N, N, N', N
There are aliphatic polyamines such as '-tetramethyl-1,3-butanediamine.

Other conventional formulation ingredients, such as silicone oils or foam stabilizers, also known as emulsifiers, may be used as desired. The foam stabilizer may be an organosilane or a siloxane. For example, a compound with the following chemical formula can be used: R3i[0-(RzSiO)z-(oxyalkylene)ffi.

In the formula, R is an alkyl group containing 1 to 4 carbon atoms, n is 4 to 8, m is 20 to 40, and the oxy and alkylene groups are derived from propylene oxide and ethylene oxide. (e.g. US-A-31947
(See No. 73).

Materials coated by the method of the invention include, for example, strands of material such as wire, glass, fibers and rods.

By the method according to the invention, crushed glass, polyester roving, cotton roving (cellulose material), rayon (cellulose acetate), ceramic roving, graphite roving, Gukron (polyethylene terecrate), NOMEX [poly(m-phenylene) isophthalate)], and KEVL
It has been found that fillers such as AR [poly(p-phenylene terephthalate)] can be introduced into two-component polyurea elastomer systems by feeding them into the spray pattern of the polyurea elastomer. This process requires, for example, that one component has 50% of its active hydrogen.
The above is in the form of amine hydrogen and contains an amine-terminated polyether with a molecular weight of 1500 or more and a chain extender,
It can be carried out using a two-component spray system in which the other component contains an aromatic polyisocyanate, which may of course be a quasi-prepolymer. When the two components are sprayed simultaneously and the filler is introduced into the spray pattern as described in the example below, the reaction is so rapid that the resulting elastomer in the filler container hardens rapidly. In one particular embodiment of the invention, a device for delivering crushed glass or other filler material is attached to a spray gun that brings together the two streams described above to deliver the filler material into a spray pattern. This filling material is, for example, 0.25 to 1.5 inches (6 to 40 m
This glass material, which can be crushed glass of any length such as
This will improve the characteristics of The fast reactivity of polyurea elastomer systems, combined with the presence of crushed glass, allows the preparation of numerous items such as bathtubs, shower stalls, small auto parts or molds where fiberglass resins, epoxy and polyester systems are currently used. It provides a more efficient way to do so.

Similarly, because of the fast reactivity and high curing rate of polyurea elastomers, molds with the required toughness can be quickly and easily prepared using crushed glass or similar fillers. These molds are easier to prepare than current methods using fiberglass resins or epoxies, which require long processing and curing times.

The following examples illustrate the invention. Percentages are parts by weight unless specified to the contrary.

EXAMPLE A spray-applied polyurea elastomer system prepared by mixing Components A and B in a high-pressure spray apparatus was prepared using an external and tacked glass roving that fed crushed fiberglass rovings into the polyurea elastomer spray pattern. Can be used in combination with chopper. The fiberglass roving can be broken into lengths of 0.25 to 1.25 inches (6 to 30 mm) and fed into a sprayed polyurea elastomer pattern before contacting the substrate. quasi-prepolymers of incyanate and high molecular weight polyols. A
The components are mixed with component B, which is a mixture of amine-terminated polyoxyalkylene diols and/or triols and amino-terminated chain extenders to obtain a polyurea elastomer. The spray polyester containing crushed glass is then sprayed into open molds for the manufacture of parts such as automobile parts, bathtubs, shower stalls or boat hulls where fiberglass resins, epoxies and polyester systems are currently used. Urea elastomers can be used. These systems, polyurea elastomers and externally added crushed glass, also
It can also be used for manufacturing molds. The major advantages of spray polyurea elastomers containing crushed glass are processing speed and flexibility, excellent mold surface quality, and excellent physical properties.

In the first embodiment of Kaiyu, l5ONATE 143L (6
0 parts) and 140% of THANOL SF 5504 as component A, JEFFAMINE D-4
000 (44, 9 copies), JEFFAMINE T-30
00 (11, 7 parts), JEFFAMINE D-2
000 (10.4 parts), diethyltoluenediamine (1
A system was used in which component B was a mixture of 0.0 parts) and N,N'-bis(t-butyl)ethylenediamine (23.0 parts).

These components were mixed in a volume ratio of 1:1 (weight ratio A:B 1.125
) to produce a polyurea elastomer. Gusm Venus glass chopper
I attached it to my GX-7 spray gun. This is 1.
The glass chopper, which feeds 25 inches (32 mm) of crushed glass roving into the polyurea elastomer spray pattern, is adjustable to provide a variable crushed glass output. This system performed extremely well with excellent wet strength. Polyurea elastomers have fast system reactivity (
1.8 seconds of gel) to "infiltrate" the predicted glass.
It didn't work, but it didn't work. The physical properties of straight spray polyurea elastomer and glass containing polyurea elastomer are shown in Table 1. Table 1 shows the effect of crushed glass in polyurea elastomers on bending modulus and thermal properties (thermal sag).

Percentage of surface glass (%) Tensile, psi [MPa] 3.95 2.19 (11,97) (13,25] (10,74
) Elongation (%) Tear, Pli fN/M) (791,61 Shore D Hardness 0 sec 60 1 part sec 51 Bending Modulus, psi (MPa) Below 77 40936 (25°C) (282,251 158'F 30775 ( 80℃)
+212.19) -20 below 86653 (-29℃) +597.47) +1005.2) (856,41 (463,011 (332,571 (313,83) (269,07) (798,351 (608, 531 Impact, notch [ft-lb/inch fJ/m) ] 7.83
7.06 7.53 (418,01F
376,91 (402,0) week l Another example is l5onate 143L (60 parts) and THANOL SF 5505 (40 parts quasi-prepolymer as component A, JEFFAMINE D-40
00 (63, 2 parts), Ethacure 300 (1
A system was used in which component B was a mixture of 5.5.2 parts) and diethyltoluenediamine (21.6 parts). A component and B
The components were mixed at a volume ratio of 11 (weight ratio A:B 1.113),
Mixing was performed using a high pressure spray device. This system is also V
It was processed using a EUS glass chopper and performed well, with a relatively slow "wetting" of the glass due to its slower reactivity, with a gel time of 2.0 seconds.

The results of the physical properties of this elastomer system are shown in Table 2.

Table 2 Bow 1 Bow length, psi (MPal Elongation (%) Tear, Pli [N/M) Shore D hardness 0 seconds 10 seconds Bending modulus, psi (MPal 77°F (25°C) 35142 (242,3'1
158 below (70°C) 24772 (170,8)-2
06F (-29℃1 91988(634,3)1
976 (13,62) 459 F2O3,81 1757 (12,11) 483 (845,9] 94548 (651,9) 73089 (503,91 123480 (851,4) Heat sag (mm) Kaiyu Another example JEFFAMINE D- uses quasi-prepolymer of l5onate 143L (60 parts) and TIIANOL 5F-5505 (40 parts) as A component.
4000 (48, 8 copies), JEFFAMINE T-3
000 (18, 3 parts), diethyltoluenediamine (1
A system was used in which component B was a mixture of 7.1 parts) and N,N'-bis(1,-butyl)ethylenediamine (15.8 parts). Component A and component B in a 1:1 volume ratio (weight ratio A
:31.123) using a high pressure spray device. This system was processed as described above in a Venus glass chopper, resulting in an elastomer with a gel time of 2.0 seconds. The results of the physical properties of this elastomer system are shown in Table 3.

11 bb- to I/60 min (> 75 mml Table 3 A Glass percentage (%) 0 Tensile, psi (MPa) 1151 (7,941
Elongation (%) 53 30 tear, Pi i (N/Ml 192 f33
6.2) Shore D hardness sec 52 1O sec 39 Bending modulus, psi (MPa) 77'F (25°Cl 33056 f227.
91158 lower (70℃) 19647 (135
,5)-20'F C-29℃1 96416F66
4.815.68 1676 (11,561 211F369.51 62705 (432,41 41463 (285,9) 110641 (762,9) Heat sag, (mm) 100m+n-250 below (121℃) 760 minutes 150mn+-250 below (121°C) 760 minutes 100mnr311”F (155°C) 760 minutes 150mm-311 (155°C) 760 minutes 21.4 54.0 ★ ★ ★Complete slack, 0.4 6.1 7.5 27. 0 > 75 mm The system in Table 3 was also used to prepare molds for polyurethane foam processing. Rigid polyurethane foam deer heads used in taxidermy operations were coated with a mold release agent. The foam was then A thin layer of polyurea elastomer was applied to completely encapsulate the material, with a total thickness of approximately 0.5
until ~0.75 inch (12.7-19 mm)
More spray polyurea elastomer was applied in combination with crushed glass to incorporate strength. After spraying
The mold was then cut lengthwise into two halves and the foam removed. The inside of the mold held the same surface as the polyurethane foam deer head. This mold was very similar to that made with fiberglass resin and fiberglass, except that it was prepared in an instant. The inside of this mold was then coated with a mold release agent, clamped together, and used to prepare a rigid polyurethane foam deer head.

All spraying operations were performed using a Gusmer HV proportioner with a Gx-7 type spray gun. For the broken glass work, a Venus R84 glass roving cutter was used. The system is 160° on the A component side.
F (71°C), the B component side used a block temperature of 150 below (65.5°C) and was sprayed with a hose temperature of 160°F (71°C). The outfoot of the system is 2 on the A component side.
500~2800psig (17.3~19.4MP
a), 2000 to 2500 psig on the E component side (
17.5 at line pressure of 13.9~19.4MPa)
~22.5 lbs/min (8-10 kg/min).

The systems were mixed in a 1:1 volume ratio in this spray device.

Satobase 2l5l5ONATE @ 143L-Dow Chemic
Modified pure DI THANOL 5F-5505-ARCOCchemi manufactured by al Co.
manufactured by Cal Company Polyoxyalkylene triol with a molecular weight of 15000, JEFFAMINE D-4000 - amino-terminated polyoxyalkylene diol with a molecular weight of 4000, JEFFAMINE T-3000 - molecular ffi 30
00 amino-terminated polyoxyalkylene diol, JEFFAMINE■ D-2000-molecular weight 2000
Amino-terminated polyoxyalkylene diol, JEFFAMINE■300-Ethyl Corpo
Di(methylthio)-toluenediamine manufactured by Ration, JEFFAMINE T-5000-Texaco C
molecular weight 500 (l) manufactured by Chemical Company.
amine-terminated polyoxyalkylene, diethyltoluenediamine N N'-bis(t-butyl)-ethylenediamine- from DETDA-Ethyle Corporation.
Glass roving made by Virginia Chemical
Made by Owens Corning Fiberglass.

Claims (4)

[Claims] (1) Produced by spraying two reactive streams together to deliver filler material into a spray pattern;
One of the two reactive streams contains a spray elastomer containing an aromatic polyisocyanate and the other reactive stream contains a spray elastomer containing an aromatic polyisocyanate having a molecular weight greater than 1500 prepared by reductive amination of a polyol. A spray elastomer, characterized in that it contains an amine-terminated polyether in which at least 50% of the active hydrogens are in the form of amine hydrogens, and a chain extender. (2) The chain extender is 1-methyl-3,5-diethyl-
2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,5,3',5'
-tetraethyl-4,4'-diaminodiphenyl-methane or 1-methyl-3,5-diethyl-2,4-diaminobenzene and 1-methyl-3,5-diethyl-2,6
2. The spray elastomer of claim 1, which is a mixture of -diaminobenzene. (3) The chain extender has the following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, x+y+z is approximately 5.3) The spray elastomer according to claim 1, comprising: (4) The chain extender has the following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (Note that here x is approximately 2.6 or approximately 5.6) The spray elastomer according to claim 1, comprising: